CN1046356A - The preparation method of film of multicomponent metal oxide - Google Patents
The preparation method of film of multicomponent metal oxide Download PDFInfo
- Publication number
- CN1046356A CN1046356A CN 90105788 CN90105788A CN1046356A CN 1046356 A CN1046356 A CN 1046356A CN 90105788 CN90105788 CN 90105788 CN 90105788 A CN90105788 A CN 90105788A CN 1046356 A CN1046356 A CN 1046356A
- Authority
- CN
- China
- Prior art keywords
- film
- target
- tio
- substrate
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The present invention adopts multiple ion-beam reaction cosputtering device, choose high pure metal, and bimetallic alloy or bimetal splicing target etc. are as target, make the substrate rotation and it is being carried out under the condition of heat, by energy and the line of controlling each plasma sputter source, select suitable working gas and air pressure, PbO, the TiO of even fine extension of growing and preparing on the throne or preferred orientation on different substrate materials
2, PbTiO
3, Pb (Zr, Ti) O
3, (Pb, La) TiO
3And PbTiO
3/ (Pb, La) TiO
3Deng the metal oxide film of unit, double base or multicomponent, and the film with different superstructures.
The present invention can accurately control film composition, and process stabilizing, and good reproducibility is easy to grasp, and is suitable for producing in batches.
Description
The invention belongs to electric light, piezoelectricity ferro that adopts multiple ion-beam reaction co-sputtering technology growing and preparing high-quality on the throne extension or preferred orientation and unit, double base and film of multicomponent metal oxide, as PbO, TiO with superstructure
2, PbTiO
3, Pb(Zr, Ti) O
3, (Pb, La) TiO
3And PbTiO
3/ (Pb, La) TiO
3Deng.
The electric light of multicomponent, piezoelectric-ferroelectric thin film as titanium (zirconium) lead plumbate lanthanum [PL(Z) T] film, all have important use and are worth in photoelectron technology and other high-tech sector.But it is big to prepare this class film difficulty, and particularly the composition of film and structure are wayward, so that poor repeatability, is unsuitable for producing.At present, prepare this class film, mainly adopt the preparation method of rf magnetron sputtering composite oxides target and many targets magnetic control reaction cosputtering.Japanese Journal of Applied Physics for example, 24, (1985), Suppl.24-3, PP.13-16 have put down in writing and have adopted the preparation of many targets magnetic control reaction co-sputtering technology (Pb, La) TiO
3Electro-optic film, this method is that three magnetron cathodes are housed in its sediment chamber, on each negative electrode, place the metallic target relevant with film component, three targets converge on the substrate, control the power of each magnetic controlling target respectively, the sputter rate of may command respective target, aerating oxygen, and substrate is heated to more than 650 ℃, realization response cosputtering film forming.The Japanese has prepared (Pb, La) TiO with this method
3With (Pb, La) TiO with superstructure
3/ PbTiO
3Film [see Japanese Journal of Applied Physics, 26, (1987), Suppl.26-2, pp.15-17].But the operating air pressure of this method is higher, and three targets have interference each other during sputter, and sputtering parameter is also wayward.
On November 9th, 1988, proposed by the inventor that a kind of (number of patent application is: 88109745.4) with the film forming device patent application of ion beam reactive sputtering method, three to four plasma sputter sources are set in the target chamber of this device, adopt the Kaufman ion source, with the substrate is that central distribution is around substrate, correspondingly in the place ahead that each ion source line penetrates be provided with one group of bobbing target, the cross section of bobbing target is a rectangle, be fixed with several piece target sheet on every group of target, can use metal, semi-conductor, isolator or organic materials are made target, be provided with an irradiate ion source that is used for the no filament cathode of irradiation substrate facing to substrate, in order to feed sputter gas and reactant gases.During film forming, the corresponding one group of target sheet of ion beam bombardment that the plasma sputter source produces, control the parameter of each ionic fluid respectively, make the material that sputters on the differing materials target sheet be deposited on the multicomponent film that forms predetermined composition ratio on the substrate simultaneously, and bobbing target as required, change the array mode of respectively organizing target, then can make multicomponent multilayer film.
The objective of the invention is to adopt multiple ion-beam reaction cosputtering device, a kind of new technology that can accurately control even high-quality multicomponent sull multicomponent sull component and structure, growing and preparing extension on the throne or preferred orientation is provided, in order to electro-optic film, piezoelectric-ferroelectric thin film for preparing multicomponent and film, also can be used for preparing unit or double base sull with superstructure.
The present invention is achieved in that (application number is 88109745.4) multiple ion-beam reaction cosputtering device that adopts inventor's design, three to four plasma sputter sources are set on this device, three to four high pure metal targets of difference sputter, perhaps one of them is bimetallic alloy target or bimetal splicing target, the material that sputters out from three or four targets converges on the substrate surface, before film forming, substrate is carried out pre-sputter clean facing to the 4th of substrate or the 5th ion source, in film process, dynamically mix to improve film quality.Adopt different substrate materials, during sputter, make substrate rotation and substrate heated (room temperature to 800 ℃ adjustable), via special ventpipe or (with) feed reactant gases via the 4th or the 5th ion source, and by control with regulate following condition and parameter:
(1) target footpath φ 60mm
(2) between target and the substrate apart from 120mm
(3) the base vacuum degree 4 * 10
-4Pa
(4) working gas Ar/O
2=1/0.2-1/1
(5) operating air pressure 3-8 * 10
-2Pa
(6) substrate rotating speed 10-120 rev/min
(7) underlayer temperature is 550 ℃-750 ℃
(8) rate of film build 100-200
/ minute
(9) plasma sputter source energy 0.3-1.2KeV
Plasma sputter source beam current density 2-12mA/cm
2
Can growing and preparing component on the throne adjustable, have preferred orientation or an epitaxially grown film of multicomponent metal oxide.Simultaneously, by control or the sputter number of adjusting high pure metal target and the sputtering parameter of each target, perhaps change target, also can prepare required different varieties and have unit, the double base sull of different physical characteristics, and the metal oxide film of multicomponent, to satisfy different service requirementss.
Further specify specific embodiments of the invention below in conjunction with accompanying drawing:
Fig. 1 is the multiple ion-beam reaction cosputtering schematic diagram of device that the present invention adopts.
Fig. 2 is the PbTiO of orientation fully that adopts the present invention's preparation
3The X-ray diffractogram of film.
Fig. 3 is (Pb, La) TiO of orientation fully that adopts the present invention's preparation
3The X-ray diffractogram of film.
In Fig. 1, garden cylindricality target chamber 1 links to each other with vacuum system 2, on target chamber, evenly dispose three focus type plasma sputter sources 3, three target holders 4 are set respectively above the plasma sputter source, placing high pure metal target Pb(purity on the target holder is 99.999%), La(99.9%) and Ti(99.9%), it is 2 * 10 that vacuum system makes the base vacuum of target chamber
-4Pa, by airing system 5 or (with) ion source 6 of irradiation substrate, making operating air pressure is 1-8 * 10
-2Pa, working gas are high-purity Ar, and reactant gases is high-purity O
2Substrate bracket 7 changes rotation with per minute 10-120, and lining heat 8 is heated to 550 °-750 ℃ with substrate 9.Before the spatter film forming, cover substrate 9 with plate washer 10 earlier, utilize plasma sputter source 3 earlier target material surface to be carried out sputter, remove the zone of oxidation on high-purity metal target surface, turn off the plasma sputter source then.Utilize 6 pairs of substrate surfaces of irradiation substrate ion source to carry out pre-washing.Substrate can be selected the α-Al of (001) for use
2O
3, or the silicon single crystal of (111), or suitable SrTiO
3, devitrified glass etc., and polish processing such as cleaning in advance.If a metallic target of a sputter (as Ti) can prepare TiO by reactive sputtering
2Film is used among light laser window protection etc.; As a splash-proofing sputtering metal Pb, then can prepare the PbO film that is used for conductron; If while two kinds of metallic targets of cosputtering (as Pb and Ti) can be by the PbTiO of reactive sputtering growing epitaxial on the throne or preferred orientation
3Film; If cosputtering three kinds of metal Pb, La and Ti simultaneously, but then (Pb, La) TiO of reactive sputtering growing epitaxial on the throne or preferred orientation
3Film.The sputter rate of each constituent element, thereby the composition of multi-element metal oxide film, can be with reference to the sputtering yield of single ion beam sputtering metallic target, parameter (as operating voltage, line) by regulating each plasma sputter source etc. is regulated, and can realize by computer control.For example, at preparation (Pb, La) TiO
3During thin-film material, be if get molecular formula
Pb
1-xLa
xTi
1-x/4O
3
When regulating La content and be about 10mol%, then can prepare and have the film that heat-flash is released electrical effect; When adjusting La content is 20-23mol%, can prepare film with strong electrooptic effect; When adjusting La content is 26-28mol%, can prepare film with strong quadratic electro-optical effect.Alternately repeat to implement above-mentioned sputter procedure, can prepare PbTiO
3/ (Pb, La) TiO
3, PbTiO
3/ TiO
2, PbO/(Pb, La) TiO
3Or the like have a film of superstructure.Like this, under the condition that does not change any target, utilize the same system can growing and preparing multi-series on the throne, many components or have the high-quality extension of different superstructures or the film of preferred orientation, to adapt to different application requiring.
Adopt the present invention's preparation uniform lead titanate (PbTiO of orientation fully
3) and load lanthanium titanate [(Pb, La) TiO
3] sputtering condition of film is listed in the table below.
Target metallic lead (Pb, purity 99.999%)
Metal titanium (Ti, purity 99.9%)
Lanthanoid metal (La, purity 99.9%)
Target diameter φ 60mm
Target and substrate distance 120mm
Working gas Ar/O
2=1/0.2-1/1
Operating air pressure 3-8 * 10
-2Pa
10-120 rev/min of substrate rotating speed
Underlayer temperature 600-750 ℃
Plasma sputter source parameter Pb target sputter: ion energy 0.3-0.6KeV
Beam current density 2-6mA/cm
2
Ti target sputter: ion energy 0.8-1.2KeV
Beam current density 5-12mA/cm
2
La target sputter: ion energy 0.4-0.7KeV
Beam current density 5-8mA/cm
2
Rate of film build 100-200
/ minute
After sputter finishes, close sputter gas Ar, keep underlayer temperature under the high temperature of setting (650 ℃), continue to feed reactant gases about 10-30 minute, help to generate the multicomponent sull of complete preferred orientation or extension.
Fig. 2 and Fig. 3 are the PbTiO that adopts the present invention's preparation
3Ferroelectric membranc and (Pb, La) TiO
3The X-ray diffractogram that electro-optic film (La content is about 28mol%) obtains under following experiment condition.
Experiment condition: Cu target, curved product graphite monochromator
35KV * 15mA, sweep velocity: 4 °/min
Chart speed: 10mm/min, T=0.1, CPS:2 * 10
4With 1 * 10
4
Sweep limit: 11 °-92 °
DS:1 °, SS:2 °, RS:0.15mm
The present invention not only can or regulate the sputter number of high pure metal target and the sputtering parameter of each target by control, growing and preparing multi-series on the throne, polycomponent and high-quality extension or preferred orientation sull under the condition that does not change target with multiple superstructure, and can prepare the electro-optic film and the piezoelectric-ferroelectric thin film of different varieties, different physical characteristics by changing target.As replace high pure metal La with high pure metal Zr, then can growing and preparing on the throne go out the Pb(Zr of the extension or the preferred orientation of different components, Ti) O
3Series thin film and relevant superlattice film.Splice target (its proportioning is controlled by two kinds of metals area occupied on target surface) if one of three targets are elected as the bimetallic alloy target or the bimetal of a certain proportioning, can prepare more complicated electro-optic film of composition and piezoelectric-ferroelectric thin film.In like manner, if adopt four focusedion sources, four metallic targets of sputter respectively, wherein three are respectively High Purity Gold Pb, Ti, Zr, and another is bimetallic alloy target or bimetal splicing target, then can prepare the three component system PbTiO of multi-series
3-PbZrO
3-Pb(M, N) O
3Electro-optic film and piezoelectric-ferroelectric thin film (M, N are certain combination of two kinds of metals), to satisfy the application requiring of different field.
The present invention compared with prior art has following advantage:
1. compare with many targets magnetic control reaction cosputtering, operating air pressure is low by (10-2Pa), few to the membrane material pollution, because low energy ion beam is little to membrane damage, at the indoor no plasma of major sedimentary, there are not the problems such as plasma bombardment substrate bracket, vacuum chamber, target, substrate, be easy to prepare high-quality thin-film;
2. the parameter in three plasma sputter sources can independently be controlled, and no phase mutual interference, and process stabilizing are easy to adjust, good reproducibility;
3. the ion gun that utilizes no filament can be removed substrate performance impurity and mechanical damage at film forming pre irradiation substrate; Irradiation and pass into reacting gas in film forming procedure can increase the chemical reaction probability, improves film performance (such as crystallinity, uniformity, attachment fastness and micro-structural). By rotating substrate, electro-optic film and the piezoelectric-ferroelectric thin film of the energy uniform extension of growth in place or preferred orientation;
4. compare with rf magnetron sputtering, the present invention can arbitrarily regulate, accurately control thin film composition, in the situation that does not change target, can prepare the high-quality thin film of multi-series, many components and the extension with different superlattice structures or preferred orientation, to satisfy different application requirements. Suitably select target, can make corresponding thin-film material with having most of piezoelectricity ferro potteries (comprising binary system and ternary system) now;
5. this method is applicable to batch production.
Claims (6)
1, adopt multiple ion-beam and react the method that the cosputtering device prepares metal oxide film, it is characterized in that on this device, being provided with three to four plasma sputter sources, three to four high pure metal targets of difference sputter, perhaps one of them is metal alloy targets or bimetal splicing target, the material that sputters out from these three or four targets converges on the substrate surface, before film forming, substrate is carried out pre-sputter clean facing to the 4th of substrate or the 5th ion source, in film process, dynamically mix to improve film quality, by making the substrate heating, rotation and select different substrate materials for use, via special ventpipe or (with) feed reactant gases via the 4th or the 5th ion source, and by control with regulate following condition and parameter:
(1) target diameter Φ 60mm
(2) between target and the substrate apart from 120mm
(3) the base vacuum degree 4 * 10
-4Pa
(4) working gas Ar/O
2=1/0.2-1/1
(5) operating air pressure 3-8 * 10
-2Pa
(6) substrate rotating speed 10-120 rev/min
(7) underlayer temperature is 550 °-750 ℃
(8) rate of film build 100-200A/ minute
(9) plasma sputter source energy 0.3-1.2KeV
Plasma sputter source beam current density 2-12mA/cm
2
Can growing and preparing on the throne go out component adjustable, have preferred orientation or an epitaxially grown film of multicomponent metal oxide, simultaneously, by regulating or the sputter number of control high pure metal target and the sputtering parameter of each target, perhaps change target, also can prepare the unit oxide compound of required different varieties and different physical characteristics, the metal oxide film of double base oxide compound and multicomponent is to satisfy different service requirementss.
2, according to the said method for manufacturing thin film of claim 1, it is characterized in that high-purity metal target is generally: purity is 99.999% Pb, 99.9% Ti, 99.9% La, or purity is the bimetallic alloy target or the bimetal splicing target of 99.9% Zr and a certain proportioning, the latter's proportioning determines that by two kinds of metals area occupied on target surface substrate material is chosen as sapphire or Si, SrTiO
3Get final product with in the devitrified glass any one.
3,, it is characterized in that in three to four metallic targets, if metallic target Ti of a sputter then can prepare TiO according to claim 1 or 2 said method for manufacturing thin film
2Film is used for light laser window protection etc., as a splash-proofing sputtering metal Pb, then can prepare the PbO film that is used for conductron, if while two kinds of metal Pb of cosputtering and Ti, can be by the PbTiO of reactive sputtering growing epitaxial on the throne or preferred orientation
3Film, if cosputtering three kinds of metal Pb, La and Ti simultaneously, but then reactive sputtering growing epitaxial on the throne or select choose to (Pb, La) TiO
3Film.
4, according to claim 1 or 2 said method for manufacturing thin film, it is characterized in that by the control and the parameter of regulating each plasma sputter source, then can prepare different physical characteristics, and sull, as at preparation (Pb, La) TiO with superstructure
3During thin-film material, getting molecular formula is Pb
1-xLa
xTi
1-x/4O
3When adjusting La content is 10mol%, then can prepare and have the film that heat-flash is released electrical effect, adjusting La content is 20-23mol% or is 26-28mol%, can prepare the film that has a strong electrooptic effect or have strong quadratic electro-optical effect, if alternately repeat to implement said process, can prepare PbTiO
3/ TiO
2, PbTiO
3/ (Pb, La) TiO
3And PbO/(Pb, La) TiO
3Deng multi-series, many components or metal oxide film with extension or preferred orientation of different superstructures.
5, according to claim 1 or 2 said method for manufacturing thin film, it is characterized in that selecting different high pure metals to make target, prepare the electro-optic film and the piezoelectric-ferroelectric thin film of different series, as replacing La with zirconium, Pb(Zr that can growth different components on the throne, Ti) O
3Series thin film and relevant superlattice film, as if the bimetallic alloy target of one of three targets being elected as a certain proportioning or bimetal splicing target, can more complicated electro-optic film and the piezoelectric-ferroelectric thin film of prepared composition.
6, according to claim 1 or 2 said method for manufacturing thin film, it is characterized in that on the ion beam reactive sputtering device, being provided with four plasma sputter sources, four metallic targets of difference sputter, wherein three are respectively high purity Pb, Ti, Zr, another is bimetallic alloy target or bimetal splicing target, then can prepare the three component system PbTiO of multi-series
3-PbZrO
3-Pb(M, N) O
3Electro-optic film and piezoelectric-ferroelectric thin film, M in the formula, N are certain combination of two kinds of metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105788 CN1024146C (en) | 1990-03-22 | 1990-03-22 | Process for preparing film of multicomponent metal oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105788 CN1024146C (en) | 1990-03-22 | 1990-03-22 | Process for preparing film of multicomponent metal oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046356A true CN1046356A (en) | 1990-10-24 |
| CN1024146C CN1024146C (en) | 1994-04-06 |
Family
ID=4879591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105788 Expired - Fee Related CN1024146C (en) | 1990-03-22 | 1990-03-22 | Process for preparing film of multicomponent metal oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024146C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366786C (en) * | 2005-08-23 | 2008-02-06 | 浙江大学 | Novel metallic film preparation technology on liquid phase substrate surface |
| CN100366790C (en) * | 2002-10-16 | 2008-02-06 | 爱发科股份有限公司 | Film forming device and film forming method |
| CN101670691A (en) * | 2005-12-29 | 2010-03-17 | 同济大学 | Antiferroelectric film with adjustable working temperature zone and higher pyroelectric coefficient and preparation method thereof |
| CN101908461A (en) * | 2010-07-08 | 2010-12-08 | 中国电子科技集团公司第十二研究所 | Ion beam surface treatment equipment and method for suppressing secondary electron emission |
| CN106939409A (en) * | 2017-03-28 | 2017-07-11 | 中山市博顿光电科技有限公司 | A kind of device and method of multi-ion source sputtering production film |
| CN107365963A (en) * | 2017-05-03 | 2017-11-21 | 四川大学 | PVD oxide coating preparation methods |
| CN109234680A (en) * | 2018-11-06 | 2019-01-18 | 南京大学 | A kind of preparation method of ultra-thin stratiform organic molecule ferroelectric thin film and the application of the ferroelectric thin film |
| CN110634749A (en) * | 2019-09-16 | 2019-12-31 | 上海师范大学 | BaSi2Epitaxial growth method of thin film |
| CN113675419A (en) * | 2021-08-20 | 2021-11-19 | 四川大学 | Surface modified titanium bipolar plate, preparation method thereof and application thereof in proton exchange membrane fuel cell |
-
1990
- 1990-03-22 CN CN 90105788 patent/CN1024146C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366790C (en) * | 2002-10-16 | 2008-02-06 | 爱发科股份有限公司 | Film forming device and film forming method |
| CN100366786C (en) * | 2005-08-23 | 2008-02-06 | 浙江大学 | Novel metallic film preparation technology on liquid phase substrate surface |
| CN101670691A (en) * | 2005-12-29 | 2010-03-17 | 同济大学 | Antiferroelectric film with adjustable working temperature zone and higher pyroelectric coefficient and preparation method thereof |
| CN101908461A (en) * | 2010-07-08 | 2010-12-08 | 中国电子科技集团公司第十二研究所 | Ion beam surface treatment equipment and method for suppressing secondary electron emission |
| CN106939409A (en) * | 2017-03-28 | 2017-07-11 | 中山市博顿光电科技有限公司 | A kind of device and method of multi-ion source sputtering production film |
| CN107365963A (en) * | 2017-05-03 | 2017-11-21 | 四川大学 | PVD oxide coating preparation methods |
| CN109234680A (en) * | 2018-11-06 | 2019-01-18 | 南京大学 | A kind of preparation method of ultra-thin stratiform organic molecule ferroelectric thin film and the application of the ferroelectric thin film |
| CN109234680B (en) * | 2018-11-06 | 2019-10-15 | 南京大学 | A kind of preparation method of ultra-thin stratiform organic molecule ferroelectric thin film and the application of the ferroelectric thin film |
| CN110634749A (en) * | 2019-09-16 | 2019-12-31 | 上海师范大学 | BaSi2Epitaxial growth method of thin film |
| CN110634749B (en) * | 2019-09-16 | 2022-03-25 | 上海师范大学 | BaSi2Epitaxial growth method of thin film |
| CN113675419A (en) * | 2021-08-20 | 2021-11-19 | 四川大学 | Surface modified titanium bipolar plate, preparation method thereof and application thereof in proton exchange membrane fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024146C (en) | 1994-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4187126A (en) | Growth-orientation of crystals by raster scanning electron beam | |
| JP4397511B2 (en) | Low resistance ITO thin film and manufacturing method thereof | |
| US6617056B1 (en) | Transparent conductive laminate, its manufacturing method, and display comprising transparent conductive laminate | |
| CN1024146C (en) | Process for preparing film of multicomponent metal oxide | |
| JPH06151930A (en) | Manufacture of chalcopyrite-type compound film | |
| CN110158034A (en) | The method of a kind of More target sputtering together preparation heterogeneity and doping than film | |
| US4874741A (en) | Non-enhanced laser evaporation of oxide superconductors | |
| CN1675400A (en) | Article coated with titanium compound film, process for producing the article and sputtering target for use in the film coating | |
| CN1459515A (en) | Multiion cluster cosputtering settling nano film apparatus | |
| JP3091599B2 (en) | Method for producing chalcopyrite type compound | |
| Xiao et al. | Epitaxial growth and crystallographic analyses of (Pb, La) TiO3 thin films by a multi‐ion‐beam reactive cosputtering technique | |
| JPH04365853A (en) | Formation of composite oxide superconducting thin film | |
| CN112640140A (en) | Method for forming film similar to perovskite material | |
| JP5035857B2 (en) | Low resistance ITO thin film and manufacturing method thereof | |
| CN112038481B (en) | Heavy rare earth doped ZnO columnar crystal preferred orientation piezoelectric film material and preparation method thereof | |
| CN101003894A (en) | Method for preparing transparent Zn0 film, and product obtained | |
| JPH04132233A (en) | Cuinse2 compound thin film formation method | |
| CN1390977A (en) | Process for preparing compound film at ordinary temp | |
| US4156050A (en) | Piezoelectric crystalline films and method of preparing the same | |
| Huan-Hua et al. | Strong surface diffusion mediated glancing-angle deposition: growth, recrystallization and reorientation of tin nanorods | |
| CN1255553A (en) | Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process | |
| CN1276439A (en) | Nb-doped barium titanate film and its preparing process | |
| Ding-quan et al. | The preparation of PLT thin films by multi-ion-beam reactive co-sputtering (MIBRECS) technique | |
| CN1796593A (en) | Method for preparing film material of metal hafnium | |
| CN107881476B (en) | Superfine-grain dual-phase alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |